CN111440321B - Multifunctional alkoxy-terminated polysiloxane polymer and preparation method thereof - Google Patents
Multifunctional alkoxy-terminated polysiloxane polymer and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a method for preparing a multifunctional alkoxy-terminated polysiloxane polymer, the method comprising: putting cyclosiloxane, a silane coupling agent and water, and performing hydrolytic condensation and prepolymerization reaction, wherein a silicon atom of the silane coupling agent is connected with an alkoxy group; removing water and alcohols, then adding a catalyst, carrying out copolymerization and ring-opening polymerization, breaking the medium, and removing small molecular substances to obtain the multifunctional alkoxy-terminated polysiloxane polymer. The invention provides alkoxy-terminated polysiloxane with functional organic groups on side chains, which is prepared by a one-pot method by using a silane coupling agent and cyclosiloxane as raw materials through the processes of hydrolysis, condensation, prepolymerization, equilibrium polymerization and the like.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a multifunctional alkoxy-terminated polysiloxane polymer and a preparation method thereof.
Background
Alkoxy-terminated polysiloxane polymers are preferred as the presently preferred polymer for the dealcoholized sealant over α, ω -dihydroxy polydimethylsiloxane (107 gum) in that: the sealant of single-component package can be prepared; the hydroxyl is not present, and the structuring phenomenon caused by the hydroxyl is reduced when the filler is blended; the storage stability is good.
At present, alkoxy-terminated polysiloxane polymers are prepared from hydrogen-terminated silicone oil or alpha, omega-dihydroxy polydimethylsiloxane (107 glue), which is generally alkoxy-terminated polydimethylsiloxane, and only have reactivity on the terminal group. Meanwhile, the adopted route is mainly prepared by hydrosilylation or condensation dealcoholization of 107 silicon hydroxyl and silicon alkoxide, basic silicone oil needs to be synthesized and then functionalized, different process equipment is needed to adapt to polymerization and functionalization, and the process is complicated.
The existing preparation technology of alkoxy-terminated polysiloxane has three main types of approaches:
(1) is prepared from dimethyldichlorosilane, monomethyltrichlorosilane or trimethylchlorosilane through alcoholysis, hydrolysis, neutralization and other steps. The obtained product has the advantages of high viscosity, easy crosslinking and poor controllability; meanwhile, hydrogen chloride generated by alcoholysis or hydrolysis of chlorosilane in the production process is not easy to remove, and the production device and process have higher requirements, high risk and large environmental protection pressure.
(2) The hydrogen-terminated silicone oil is prepared by performing hydrosilylation on hydrogen-terminated silicone oil and a vinyl silane coupling agent, and the main reaction equation is as follows:
the catalyst used is generally a noble metal catalyst, and silicone oil is required to be used as a raw material, wherein a plurality of synthesis processes are involved, and direct synthesis is not adopted.
(3) The alpha, omega-dihydroxy polydimethylsiloxane is prepared by condensation dealcoholization of alpha, omega-dihydroxy polydimethylsiloxane and a multifunctional silane coupling agent, and the main reaction equation is as follows:
the method takes silicone oil as a raw material, and belongs to indirect method synthesis. Wherein, the two reaction modes (2) and (3) adopt polydimethylsiloxane as raw material, only end groups are different, and the main chain is dimethyl. The methyl group acts as a relatively reactive inert organic group, rendering the resulting alkoxy-terminated polymer reactive only at the end groups.
Patent CN 104558612B discloses that alkoxy silane is added into alpha, omega dihydroxy polydimethylsiloxane as an end-capping agent under inert atmosphere, organic amine salt is used as a catalyst, the reaction is carried out for 1 to 5 hours at the temperature of between 50 and 90 ℃, and then low molecules are removed by reduced pressure distillation, so as to obtain alkoxy end-capped polysiloxane polymer. The scheme is that alkoxy-terminated polysiloxane is prepared by condensation dealcoholization of 107 glue and a silane coupling agent.
The preparation of hydroxyl-terminated aminopropyl Silicone oils by the "one-pot process" is reported in the article "Supermolecular Silicone Elastomers with health and Hydrophobic Properties Crosslinked by" Salt-Forming vulcanzation ".
A study on the synthesis and functionalization of aminopropyl modified silicone oil by Shandong university reports that hydroxyl-terminated aminopropyl silicone oil is obtained by a one-pot method, and N is required in the reaction process2Protecting, and controlling the reaction temperature to be 90-100 ℃ to prevent the amino from being oxidized. In the process described in this paper, the catalyst (KOH), the cocatalyst dimethyl sulfoxide (DMSO), the cyclosiloxane, the silane coupling agent and water were all dosed at once. Wherein, water is a strong chain terminator, and the catalyst is added with water simultaneously to reduce the activity of the catalyst, so that dimethyl sulfoxide (DMSO) is required to be added as a cocatalyst. The existence of dimethyl sulfoxide in the system can affect the quality of the silicone oil, and complete removal cannot be guaranteed even if the low removal treatment is carried out in the later stage. In addition, KOH was chosen as the catalyst in this paper, eventually requiring acid neutralizationThe generated inorganic salt is present in the silicone oil, and the transparency of the silicone oil is lowered. Although it is mentioned that the alkoxy-terminated silicone oil can be obtained by incomplete hydrolysis and condensation of the silane coupling agent under the condition of insufficient water, experiments carried out in the paper are all one-time feeding, only water is argued, the hydrolysis and condensation process is mainly carried out under the catalysis of KOH by taking KOH as a catalyst (KOH) and dimethyl sulfoxide as a cocatalyst, the reaction is faster, the hydrolysis is more thorough, and the obtained alkoxy-terminated silicone oil is less.
In view of the above, the present invention is specifically proposed.
Disclosure of Invention
The invention provides alkoxy-terminated polysiloxane with functional organic groups on side chains, which is prepared by a one-pot method and by using a silane coupling agent and cyclosiloxane as raw materials through processes of hydrolytic condensation, prepolymerization, copolymerization, balanced ring-opening polymerization and the like.
The basic concept of the technical scheme adopted by the invention is as follows:
a method of preparing a multifunctional alkoxy-terminated polysiloxane polymer, the method comprising:
putting cyclosiloxane, a silane coupling agent and water, and performing hydrolytic condensation and prepolymerization reaction, wherein a silicon atom of the silane coupling agent is connected with an alkoxy group;
removing water and alcohols, then adding a catalyst, carrying out copolymerization and balanced ring-opening polymerization reaction, breaking the medium, and removing small molecular substances to obtain the multifunctional alkoxy end-capped polysiloxane polymer.
In one embodiment, the molar ratio of the silane coupling agent to water, n (silane coupling agent)/n (water), is 10-5～105Preferably 0.05 to 20, and more preferably 0.1 to 10.
As an embodiment, the charging molar ratio n (silane coupling agent)/n (cyclosiloxane) of the cyclosiloxane and the silane coupling agent is 10-5～105Preferably 0.01 to 100, and more preferably 0.1 to 10.
As an embodiment, the hydrolytic condensation and prepolymerization reaction belongs to an autocatalytic process, and no catalyst or cocatalyst is added.
As an embodiment, the reaction temperature of the hydrolytic condensation and the prepolymerization reaction is 50-120 ℃, the reaction time is 0.5-24h, more preferably 70-100 ℃, and the reaction time is 1-8 h.
As an embodiment, the copolymerization and the equilibrium ring-opening polymerization reaction are carried out at a reaction temperature of 50 to 180 ℃ and a reaction time of 0.5 to 24 hours.
As an embodiment, water and alcohols are removed by reduced pressure distillation under the following conditions: 50-180 deg.C, vacuum degree not more than 0.09MPa, preferably 50-120 deg.C, vacuum degree not more than 0.02 MPa.
As an embodiment, the method adopts reduced pressure distillation to remove the micromolecule substances, and adopts the following conditions: 50-180 ℃, the vacuum degree is less than or equal to 0.09MPa, preferably 140-180 ℃, and the vacuum degree is less than or equal to 0.02 MPa.
As an embodiment, the cyclosiloxane has the structure shown below:
wherein:
n + m is more than or equal to 3, and n and m are integers more than or equal to 0;
R1、R2、R3、R4are each R' (CH)2)xThe same or different groups represented;
x is an integer of more than or equal to 0, R' is one or a combination of more of hydrogen atom, amino group, sulfhydryl group, carboxyl group, halogen atom, phenyl group, trifluoropropyl group, epoxy group, vinyl group, piperazinyl group, N- (beta-aminoethyl) -gamma-aminopropyl group, gamma-glycidoxypropyl group or gamma-methacryloxy group.
Preferably, R1、R2、R3、R4Respectively one or more of aminopropyl, carboxyl, mercaptopropyl, methyl, vinyl or phenyl.
More preferably, the cyclosiloxane is one or a mixture of cyclotrisiloxane to cycloeicosasiloxane.
More preferably, the cyclosiloxane is one or a mixture of cyclosiloxanes with n + m of 3-10.
As one embodiment, the silane coupling agent has a structure as shown below:
wherein R is5、R6、R7Or R8Are each R' (CH)2)xThe same or different groups represented;
x is an integer of 0 or more;
r' is one or more of hydrogen atom, amino, sulfydryl, carboxyl, halogen atom, phenyl, trifluoropropyl, epoxy group, vinyl, N- (beta-aminoethyl) -gamma-aminopropyl, piperazinyl, gamma-glycidyl ether oxy or gamma-methacryloxy.
Preferably, R5、R6Is methyl or ethyl, R7、R8Is one or more of methyl, carboxyl, aminopropyl, N- (beta-aminoethyl) -ethylaminopropyl, piperazinyl or mercaptopropyl.
As an embodiment, the catalyst is an organic base, an inorganic base, an organometallic base, a strong protic acid, a lewis acid, or an acidic solid.
Preferably, the organic base is NaOH, KOH, LiOH, Me4NOH、Et4NOH、Bu4POH, sulfuric acid, sulfonic acid, perchloric acid, ferric chloride, stannic chloride, ion exchange resins, or acid clay.
As an implementation manner, the media breaking method includes: heating to 130 deg.C or higher to decompose the temporary catalyst, filtering to remove solid catalyst or adding neutralizing agent.
Preferably, the neutralizing agent is acetic acid, sulfuric acid, phosphoric acid, hydrochloric acid, triethylamine, ethylenediamine, ammonia water, sodium hydroxide or potassium hydroxide.
The invention also relates to a multifunctional alkoxy-terminated polysiloxane polymer obtained by the preparation method of any one of the above contents.
The present invention is also directed to a multifunctional alkoxy-terminated polysiloxane polymer having the structure described below:
wherein:
y is a x n, z is a x m, wherein n + m is more than or equal to 3, and a, n and m are integers more than or equal to 0;
R1—R8are each R' (CH)2)xThe same or different groups represented;
x is an integer of 0 or more;
r' is one or more of hydrogen atom, amino, sulfydryl, carboxyl, halogen atom, phenyl, trifluoropropyl, epoxy group, vinyl, N- (beta-aminoethyl) -gamma-aminopropyl, piperazinyl, gamma-glycidyl ether oxy or gamma-methacryloxy;
R9and R10Are each R5Or R6Wherein R is5Or R6Is the above-mentioned R' (CH)2)xOne or a combination of several of the same or different groups.
Preferably, R5、R6Is methyl or ethyl, R7、R8Is one or more of methyl, carboxyl, aminopropyl, N- (beta-aminoethyl) -ethylaminopropyl, piperazinyl or mercaptopropyl.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention directly starts from monomers by a one-pot method, and can control incomplete hydrolysis of the silane coupling agent by shortening the hydrolytic condensation time and adjusting the proportion of water and the silane coupling agent and the hydrolytic condensation time even if the water is excessive, thereby finally obtaining the alkoxy-terminated polysiloxane. The preparation process is simpler and does not need excessive intermediate product treatment and process equipment switching, which is different from the principles of the existing chlorosilane direct method, hydrosilylation method and 107 glue condensation dealcoholization method.
2. The products prepared by the invention have a plurality of reaction sites, are not limited to end groups, and have reactive groups on side groups, while the hydrosilylation method and the 107 glue condensation dealcoholization method have reactivity only on the end groups and have no reactivity on other parts because the base raw material is dimethyl polysiloxane.
3. The reaction process of hydrolytic condensation and prepolymerization does not need additional catalyst, and belongs to the autocatalysis process. Compared with the process of additionally adding a strong acid and strong base catalyst in the autocatalysis process, the alkoxy hydrolysis condensation process is slow, the reaction is controllable, partial alkoxy can still be reserved under the condition of sufficient water, and the final alkoxy-terminated product is convenient to obtain.
4. According to the invention, the catalyst is added after dehydration and dealcoholization to accelerate the reaction process, and the activity of the catalyst is not influenced by water, so that the catalyst which can be deactivated by water can be selected, meanwhile, a decomposable catalyst or a filterable solid catalyst prepared from tetramethylammonium hydroxide and the like can be used, a cocatalyst and a neutralizer are not required to be added, and the quality of the silicone oil is improved.
5. According to the invention, starting from monomers (cyclosiloxane and functional silane coupling agent) by a one-pot method, the silane coupling agent and the cyclosiloxane are put into a reaction vessel at one time, and the processes of hydrolytic condensation, prepolymerization and ring-opening polymerization are simultaneously carried out, so that the viscosity of silicone oil is controlled by adjusting the molar ratio of water to the silane coupling agent and the hydrolytic condensation time to ensure that the siloxy is not completely hydrolyzed and condensed, and finally the polysiloxane with a polysiloxane side chain having functional organic groups and an alkoxy end capping is obtained. Meanwhile, in order to prevent water and alcohol from influencing the catalyst in the reaction process, no catalyst is additionally added in the hydrolytic condensation process (taking amino silicone oil as an example, amino has alkalinity, when silicone oil with high amino content is synthesized, the alkalinity of the amino is enough to advance the hydrolytic condensation and prepolymerization process, the process belongs to autocatalysis, organic amine and proton donor (alcohol) interact to form silicon alkoxide for anion ring opening), after the prepolymerization dehydration and dealcoholization, a strong base catalyst (even alkali glue prepared by tetramethyl ammonium hydroxide is taken as the catalyst, the catalyst can be decomposed by heating without neutralization), the ring opening and equilibrium polymerization speed is improved, and the use of a cocatalyst is avoided. Strong irritant substances such as hydrochloric acid and the like are not generated in the preparation process, and the obtained product not only has alkoxy on the terminal group, but also can have functional organic groups on the main chain of the polysiloxane molecule, so that more reaction sites are provided for the subsequent functionalization of the silicone oil.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the example serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic reaction scheme of the production method of the present invention.
FIG. 2 is a nuclear magnetic resonance H spectrum of a target product prepared in example 1 of the present invention.
FIG. 3 is a nuclear magnetic resonance H spectrum of the objective product prepared in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
A method of preparing a multifunctional alkoxy-terminated polysiloxane polymer, the method comprising: putting cyclosiloxane, a silane coupling agent and water, and performing hydrolytic condensation and prepolymerization reaction, wherein a silicon atom of the silane coupling agent is connected with an alkoxy group;
removing water and alcohols, then adding a catalyst, carrying out copolymerization and balanced ring-opening polymerization reaction, breaking the medium, and removing small molecular substances to obtain the multifunctional alkoxy end-capped polysiloxane polymer. The reaction scheme is shown in figure 1.
The invention does not add extra catalyst in the hydrolytic condensation process, and adds strong base catalyst after the prepolymerization dehydration dealcoholization, thereby not only preventing the influence of water and alcohol on the catalyst, but also improving the ring opening and equilibrium polymerization speed, and simultaneously avoiding the use of cocatalyst.
The preparation method can regulate and control the incomplete hydrolysis of alkoxy into silicon hydroxyl by controlling the insufficient water quantity or the insufficient reaction time of the water quantity and the hydrolytic condensation and prepolymerization reaction, and finally obtain the alkoxy-terminated polysiloxane polymer.
When the water amount is not enough, namely calculated according to the stoichiometric ratio of the silane coupling agent to the water, when n (silane coupling agent)/n (water) > 1, the water amount is not enough, the silane coupling agent in the system can not be completely hydrolyzed into silicon hydroxyl, and the alkoxy-terminated silicone oil is finally obtained even if the hydrolytic condensation and prepolymerization reaction time is prolonged.
When the water amount is sufficient, the hydrolysis condensation and the prepolymerization reaction need time, and when the time is insufficient, the reaction can not be fully carried out, so that the hydrolysis condensation can be ensured to be insufficient by controlling the reaction time within a certain value range, and the alkoxy terminated silicone oil can be obtained.
In one embodiment of the present invention, the molar ratio n (silane coupling agent)/n (water) of the silane coupling agent to water is 10-5～105Preferably 0.05 to 20, and more preferably 0.1 to 10.
In one embodiment of the present invention, the charging molar ratio n (silane coupling agent)/n (cyclosiloxane) of the cyclosiloxane to the silane coupling agent is 10-5～105Preferably 0.01 to 100, and more preferably 0.1 to 10.
According to the invention, a silane coupling agent and cyclosiloxane are put into a reaction vessel at one time, hydrolysis, condensation, prepolymerization and ring-opening polymerization processes are carried out simultaneously, the molar ratio of water, cyclosiloxane and silane coupling agent is adjusted to ensure that siloxy is not subjected to complete hydrolysis and condensation, the viscosity of silicone oil is controlled, and finally the polysiloxane with functional organic groups on the side chains and alkoxy end capping is obtained.
As an embodiment, the hydrolytic condensation and prepolymerization reaction belongs to an autocatalytic process, and no catalyst or cocatalyst is added.
As an embodiment, the reaction temperature of the hydrolytic condensation and the prepolymerization reaction is 50-120 ℃, the reaction time is 0.5-24h, preferably the reaction temperature is 70-100 ℃, and the reaction time is 1-8 h.
When the above reaction temperature is lower than 50 ℃, the hydrolytic condensation rate is too slow, only the hydrolysis process may be present, and the prepolymerization reaction may be affected. The boiling point of methanol or ethanol generated by hydrolysis is lower than 100 ℃, and the reaction system can be refluxed at 100 ℃, so that the energy is saved, the requirement of the reaction system can be met, and the comprehensive benefit is better.
According to the invention, by adjusting the hydrolysis condensation time to the range, the siloxy is not completely hydrolyzed and condensed, especially under the condition of sufficient water, the alkoxy is not hydrolyzed fully during the hydrolysis condensation time, so that the viscosity of the silicone oil is controlled, and finally, the polysiloxane with functional organic groups on the side chains and blocked by the alkoxy is obtained.
As an embodiment, the copolymerization and the equilibrium ring-opening polymerization reaction are carried out at a reaction temperature of 50 to 180 ℃ and a reaction time of 0.5 to 24 hours.
The reaction temperature is lower than 50 ℃, copolymerization and equilibrium ring-opening polymerization cannot be carried out, and the reaction temperature exceeds 180 ℃, which may cause decomposition of the polysiloxane.
As an embodiment, water and alcohols are removed by reduced pressure distillation under the following conditions: 50-180 deg.C, vacuum degree not more than 0.09MPa, preferably 50-120 deg.C, vacuum degree not more than 0.02 MPa;
as an embodiment, the method adopts reduced pressure distillation to remove the micromolecule substances, and adopts the following conditions: 50-180 ℃, the vacuum degree is less than or equal to 0.09MPa, preferably 140-180 ℃, and the vacuum degree is less than or equal to 0.02 MPa.
As an embodiment, the cyclosiloxane has the structure shown below:
wherein:
n + m is more than or equal to 3, and n and m are integers more than or equal to 0;
R1、R2、R3、R4are each R' (CH)2)xThe same or different groups represented;
x is an integer of more than or equal to 0, R' is one or a combination of more of hydrogen atom, amino group, sulfhydryl group, carboxyl group, halogen atom, phenyl group, trifluoropropyl group, epoxy group, vinyl group, piperazinyl group, N- (beta-aminoethyl) -gamma-aminopropyl group, gamma-glycidoxypropyl group or gamma-methacryloxy group.
Preferably, R1、R2、R3、R4Respectively one or more of aminopropyl, carboxyl, mercaptopropyl, methyl, vinyl or phenyl.
More preferably, the cyclosiloxane is one or a mixture of cyclotrisiloxane to cycloeicosasiloxane.
More preferably, the cyclosiloxane is one or a mixture of cyclosiloxanes with n + m of 3-10.
As one embodiment, the silane coupling agent has a structure as shown below:
wherein R is5、R6、R7Or R8Are each R' (CH)2) x represents the same or different groups;
x is an integer of 0 or more;
r' is one or more of hydrogen atom, amino, sulfydryl, carboxyl, halogen atom, phenyl, trifluoropropyl, epoxy group, vinyl, N- (beta-aminoethyl) -gamma-aminopropyl, piperazinyl, gamma-glycidyl ether oxy or gamma-methacryloxy.
Preferably, R5、R6Is methyl or ethyl, R7、R8Is one or more of methyl, carboxyl, aminopropyl, N- (beta-aminoethyl) -ethylaminopropyl, piperazinyl or mercaptopropyl.
The above groups have acidity or alkalinity, and the hydrolytic condensation is carried out under acid or alkali conditions, so the groups can help to initiate the autocatalysis process in the hydrolytic condensation process, and further realize the autocatalysis in the hydrolytic condensation process. In addition, the groups are commonly found in many commercial products, have wide sources, are convenient to obtain, and provide more choices for reducing the production cost of target products and improving the quality.
When the silane coupling agent with amino is selected, the amino has alkalinity, when the silicone oil with high amino content is synthesized, the alkalinity of the amino is enough to promote the hydrolysis condensation and prepolymerization process, the process belongs to autocatalysis, organic amine and proton donor (alcohol) interact to form silicon alkoxide to carry out anion ring opening. Of course, silane coupling agents with acidic groups can also be selected for autocatalytic cationic ring opening.
The above autocatalytic process can be demonstrated by the fact that: the polysiloxane with high amino group content is actively degraded due to the alkalinity of aminopropyl, and the ring-opening polymerization and degradation of the polysiloxane are reversible equilibrium reactions. The self-catalysis process has weak acidity and alkalinity relative to the added catalyst, and even if the water is sufficient and the hydrolysis time is in a certain range, the silane coupling agent is hydrolyzed slowly due to the self-catalysis effect, so that the reaction is more controllable.
As an embodiment, the catalyst is an organic base, an inorganic base, an organometallic base, a strong protic acid, a lewis acid, or an acidic solid.
Preferably, the organic base is NaOH, KOH, LiOH, Me4NOH、Et4NOH、Bu4POH, sulfuric acid, sulfonic acid, perchloric acid, ferric chloride, stannic chloride, ion exchange resins, or acid clay.
When the alkali glue prepared by tetramethylammonium hydroxide is used as a catalyst, the alkali glue can be decomposed by heating without neutralization, so that the ring-opening and equilibrium polymerization speed can be increased, and the use of a cocatalyst can be avoided.
As an implementation mode, the media breaking method comprises the following steps: the temporary catalyst is decomposed when the temperature is raised to 130 ℃ or higher, and the solid catalyst is removed by filtration or a neutralizing agent is added.
The temporary catalyst is Me4NOH、Et4NOH or Bu4POH, etc., solid catalyst such as acid clay and ion exchange resin, and neutralizing agent added with corresponding acid or alkali matter based on the acidity or basicity of the catalyst.
Preferably, the neutralizing agent is acetic acid, sulfuric acid, phosphoric acid, hydrochloric acid, triethylamine, ethylenediamine, ammonia water, sodium hydroxide or potassium hydroxide.
The invention also relates to a multifunctional alkoxy-terminated polysiloxane polymer obtained by the preparation method of any one of the above contents.
The present invention is also directed to a multifunctional alkoxy-terminated polysiloxane polymer having the structure described below:
wherein:
y is a x n, z is a x m, wherein n + m is more than or equal to 3, and a, n and m are integers more than or equal to 0;
R1—R8are each R' (CH)2)xThe same or different groups represented;
x is an integer of 0 or more;
r' is one or more of hydrogen atom, amino, sulfydryl, carboxyl, halogen atom, phenyl, trifluoropropyl, epoxy group, vinyl, N- (beta-aminoethyl) -gamma-aminopropyl, piperazinyl, gamma-glycidyl ether oxy or gamma-methacryloxy;
R9and R10Are each R5Or R6Wherein R is5Or R6Is the above-mentioned R' (CH)2)xOne or a combination of several of the same or different groups.
Preferably, R5、R6Is methyl or ethyl, R7、R8Is one or the combination of a plurality of methyl, carboxyl, aminopropyl, N- (beta-aminoethyl) -ethylaminopropyl, piperazinyl or mercaptopropyl.
Example 1
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (0.94g, 0.0524mol) were added to a 500mL three-necked flask to give mixture A, which was fitted with a bulb condenser and a mechanical stirrer; heating the mixture A to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 6 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, 1 wt% of tetramethylammonium hydroxide in the alkali glue) prepared by tetramethylammonium hydroxide into the prepolymer, and carrying out copolymerization and equilibrium ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
The nuclear magnetic test spectrum of the target product is shown in FIG. 2.
1H NMR(400MHz，CDCl3):
δ(ppm)0.09(s,H,-SiCH3),
0.439-0.544(m,2H,-SiCH2CH2CH2N-),
1.1-1.15(t,-SiOCH2CH3),
1.38-1.44(m,2H,-SiCH2CH2CH2NH2),
2.536-2.614(t,2H,-SiCH2CH2CH2NH2),
3.64-3.69(m,-SiOCH2CH3)。
Example 2
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (0.94g, 0.0524mol) were added to a 500mL three-necked flask to give mixture A, which was fitted with a bulb condenser and a mechanical stirrer; heating the mixture A to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 4 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, 1 wt% of tetramethylammonium hydroxide in the alkali glue) prepared by tetramethylammonium hydroxide into the prepolymer, and carrying out copolymerization and equilibrium ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 3
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (0.94g, 0.0524mol) were added to a 500mL three-necked flask to give mixture A, which was fitted with a bulb condenser and a mechanical stirrer; heating the mixture A to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 2 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, 1 wt% of tetramethylammonium hydroxide in the alkali glue) prepared by tetramethylammonium hydroxide into the prepolymer, and carrying out copolymerization and equilibrium ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst for catalyst breaking; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 4
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (1.89g, 0.105mol) were added to a 500mL three-necked flask to give mixture A, fitted with a spherical condenser and a mechanical stirrer; heating the mixture A to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 2 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, the content of tetramethyl ammonium hydroxide in the alkali glue is 1 wt%) prepared by tetramethyl ammonium hydroxide into the prepolymer, and carrying out copolymerization and balanced ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 5
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (1.89g, 0.105mol) were added to a 500mL three-necked flask to give mixture A, fitted with a spherical condenser and a mechanical stirrer; heating the mixture A to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 2 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; KOH (0.098g, 0.00175mol) was then added to the prepolymer, and copolymerization and equilibrium ring-opening polymerization were carried out at normal pressure and 110 ℃ for 5 hours to obtain a polymer; the polymer was cooled to room temperature and the catalyst was neutralized by the addition of glacial acetic acid (0.107g, 0.0179 mol); and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 6
Octamethylcyclotetrasiloxane (200g,0.674 mol), mercaptopropylmethyldiethoxysilane (10g,0.0524mol), water (1.89g, 0.105mol) were added to a 500mL three-necked flask to give mixture A, which was fitted with a bulb condenser and a mechanical stirrer; heating the mixture A to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 2 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding 2g of acid clay into the prepolymer, and carrying out copolymerization and balanced ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; cooling the polymer to room temperature, filtering to remove the catalyst, and breaking the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 7
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (0.94g, 0.524mol) were added to a 500mL three-necked flask to give mixture A, fitted with a spherical condenser and a mechanical stirrer; heating the mixture A to 80 ℃ gradually under the heating of an oil bath, and carrying out hydrolytic condensation and prepolymerization reaction by refluxing and stirring for 1 hour to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, the content of tetramethyl ammonium hydroxide in the alkali glue is 1 wt%) prepared by tetramethyl ammonium hydroxide into the prepolymer, and carrying out copolymerization and balanced ring-opening polymerization reaction for balancing for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Examples 8 to 10
The present examples 8 to 10 differ from example 1 in that: the examples of n (silane coupling agent)/n (water) and n (silane coupling agent)/n (cyclosiloxane) are shown in Table 1.
TABLE 1
| n (silane coupling agent) | n (Water) | n (cyclosiloxane) | |
| Example 8 | 0.209 | 0.0209 | 0.674 |
| Example 9 | 0.067 | 0.1 | 0.674 |
| Example 10 | 0.209 | 0.209 | 0.021 |
Example 11
This example differs from example 1 in that different cyclosiloxanes (tetraaminopropyltetramethylcyclotetrasiloxane) and silane coupling agents (N- (. beta. -aminoethyl) -. gamma. -aminopropylmethyldimethoxysilane) and charge ratios were used, while changing the charge molar ratio N (silane coupling agent)/N (water) used in the hydrolytic condensation reaction.
Tetraaminopropyltetramethylcyclotetrasiloxane (310g, 0.674mol), N- (. beta. -aminoethyl) -gamma. -aminopropylmethyldimethoxysilane (10.81g, 0.0524mol), water (1.41g, 0.0786mol) were added to a 500mL three-necked flask to give a mixture A, which was equipped with a spherical condenser and a mechanical stirrer; heating the mixture A to 90 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 6 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, the content of tetramethyl ammonium hydroxide in the alkali glue is 1 wt%) prepared by tetramethyl ammonium hydroxide into the prepolymer, and carrying out copolymerization and balanced ring-opening polymerization reaction for 4 hours at normal pressure and 100 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 12
This example differs from example 1 in that a different cyclosiloxane (tetravinyltetramethylcyclotetrasiloxane) and silane coupling agent (piperazinylmethyldimethoxysilane) were used.
Adding tetravinyltetramethylcyclotetrasiloxane (232g, 0.674mol), piperazinylmethyldiethoxysilane (13.6g, 0.0524mol) and water (0.94g, 0.0524mol) into a 500mL three-neck flask to obtain a mixture A, and installing a spherical condenser tube and a mechanical stirrer; heating the mixture A to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 6 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, 1 wt% of tetramethylammonium hydroxide in the alkali glue) prepared by tetramethylammonium hydroxide into the prepolymer, and carrying out copolymerization and equilibrium ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 13
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (0.94g, 0.0524mol) were added to a 500mL three-necked flask to give mixture A, which was fitted with a bulb condenser and a mechanical stirrer; heating the mixture A to 50 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 24 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, 1 wt% of tetramethylammonium hydroxide in the alkali glue) prepared by tetramethylammonium hydroxide into the prepolymer, and carrying out copolymerization and equilibrium ring-opening polymerization reaction for 0.5 hour at normal pressure and 120 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 14
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (0.94g, 0.0524mol) were added to a 500mL three-necked flask to give mixture A, which was fitted with a bulb condenser and a mechanical stirrer; heating the mixture A to 120 ℃ gradually under the heating of an oil bath, and carrying out hydrolytic condensation and prepolymerization reaction by refluxing and stirring for 1 hour to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, 1 wt% of tetramethylammonium hydroxide in the alkali glue) prepared from tetramethylammonium hydroxide into the prepolymer, and carrying out copolymerization and balanced ring-opening polymerization reaction for 24 hours at normal pressure and 80 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Example 15
Octamethylcyclotetrasiloxane (200g,0.674 mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (1.88g, 0.1048mol) were added to a 500mL three-necked flask to give mixture A, which was fitted with a spherical condenser and a mechanical stirrer; heating the mixture A to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 8 hours to obtain a mixture B; cooling the mixture B to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01MPa to obtain a prepolymer; then adding alkali glue (1g, 1 wt% of tetramethylammonium hydroxide in the alkali glue) prepared by tetramethylammonium hydroxide into the prepolymer, and carrying out copolymerization and equilibrium ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
Comparative example 1
Octamethylcyclotetrasiloxane (200g), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (0.94g, 0.0524mol), an alkali gum prepared from tetramethylammonium hydroxide (1g, 1 wt% of tetramethylammonium hydroxide in the alkali gum) and DMSO (1.0g) were added to a 500mL three-necked flask to obtain a mixture X, which was equipped with a spherical condenser and a mechanical stirrer; heating the mixture X to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 4 hours to obtain a mixture Y; cooling the mixture Y to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01 MPa; then carrying out copolymerization and balanced ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature.
Comparative example 1 the catalyst was added at the time of hydrolytic condensation, and the catalyst lost activity by the influence of water, so that the ring-opening polymerization could not proceed.
Comparative example 2
This comparative example differs from example 1 in that: the amount of water used, and the time of reflux stirring for the hydrolytic condensation and prepolymerization reactions were varied.
Octamethylcyclotetrasiloxane (200g,0.6742mol), aminopropylmethyldiethoxysilane (10g,0.0524mol), water (1.89g, 0.105mol) were added to a 500mL three-necked flask to give mixture M, which was fitted with a spherical condenser and a mechanical stirrer; heating the mixture M to 100 ℃ gradually under the heating of an oil bath, and carrying out hydrolysis condensation and prepolymerization reaction by refluxing and stirring for 48 hours to obtain a mixture P; cooling the mixture P to room temperature, and removing ethanol and residual water generated by hydrolysis in the system by a reduced pressure distillation mode at the temperature of 50 ℃ and the pressure of 0.01 MPa; then adding alkali glue (1g, 1 wt% of tetramethylammonium hydroxide in the alkali glue) prepared by tetramethylammonium hydroxide into the prepolymer, and carrying out copolymerization and equilibrium ring-opening polymerization reaction for 5 hours at normal pressure and 110 ℃ to obtain a polymer; heating to 140 ℃, preserving the temperature for 30 minutes, and decomposing the catalyst to break the catalyst; and finally, removing the micromolecule low-boiling products in the system by reduced pressure distillation at 180 ℃ and under the pressure of 0.01MPa, keeping the vacuum condition, and cooling to room temperature to obtain the target product.
The nuclear magnetic test spectrum of the target product prepared in comparative example 2 is shown in fig. 3.
The results of nuclear magnetic tests showed that the characteristic peak of ethoxy group was apparently disappeared, indicating that in the case where the amount of water input and the hydrolytic condensation time were different from those of the present application, alkoxy group was completely hydrolyzed to silicon hydroxy group, and finally hydroxyl group-terminated polysiloxane was obtained, and the multifunctional alkoxy group-terminated polysiloxane polymer described in the present invention could not be obtained.
The relevant performance parameters of the products prepared in examples 1-15 and comparative examples 1-2 above are shown in table 2 below.
TABLE 2
By comparing the examples of the invention with the comparative examples, the following conclusions are drawn:
1. according to nuclear magnetic tests, the alkoxy-terminated silicone oil with various functional groups is prepared by controlling the water quantity or/and the reaction time conditions of hydrolytic condensation and prepolymerization reaction;
2. the invention avoids catalyst deactivation by autocatalysis and adding catalyst in the stage of equilibrium ring opening, while the preparation method of the comparative example 1 has catalyst deactivation and no polymerization;
3. the appearance of the silicone oil which is subjected to neutralization is turbid, and a part of the preferred embodiments of the invention use a temporary catalyst or a filterable catalyst, so that the silicone oil is transparent and has better performance;
4. the invention can obtain the silicone oil with different viscosities by controlling the reaction conditions, has richer product types, meets different requirements of users,
although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (22)
1. A method of preparing a multifunctional alkoxy-terminated polysiloxane polymer, comprising:
putting cyclosiloxane, a silane coupling agent and water, and performing hydrolytic condensation and prepolymerization reaction, wherein a silicon atom of the silane coupling agent is connected with an alkoxy group;
removing water and alcohols, then adding a catalyst, carrying out copolymerization and balanced ring-opening polymerization reaction, breaking the medium, and removing small molecular substances to obtain the multifunctional alkoxy end-capped polysiloxane polymer;
the hydrolytic condensation and prepolymerization reaction belongs to an autocatalysis process, and a catalyst and a cocatalyst are not added;
the feeding molar ratio n (silane coupling agent)/n (water) of the silane coupling agent to water is 10-5 ~ 105；
The reaction temperature of the hydrolysis condensation and the prepolymerization reaction is 50-120 ℃, and the reaction time is 0.5-24 h;
the silane coupling agent has the following structure:
wherein R is5、R6Are each R' (CH)2)xThe same or different groups represented;
x is an integer of 0 or more;
r' comprises one or more of hydrogen atom, amino group, sulfhydryl group, carboxyl group, halogen atom, N- (beta-aminoethyl) -gamma-aminopropyl and piperazinyl;
R7、R8is one or more of methyl, carboxyl, aminopropyl, N- (beta-aminoethyl) -ethylaminopropyl, piperazinyl or mercaptopropyl, and R7And R8Not methyl at the same time.
2. The production method according to claim 1, wherein the molar ratio n (silane coupling agent)/n (water) of the silane coupling agent to water is 0.05 to 20.
3. The method according to claim 2, wherein the molar ratio n (silane coupling agent)/n (water) of the silane coupling agent to water is 0.1 to 10.
4. The method according to claim 1, wherein the charging molar ratio of the cyclosiloxane to the silane coupling agent, n (silane coupling agent)/n (cyclosiloxane), is 10-5 ~ 105。
5. The method according to claim 4, wherein the charging molar ratio n (silane coupling agent)/n (cyclosiloxane) of the cyclosiloxane to the silane coupling agent is 0.01 to 100.
6. The method according to claim 5, wherein the charging molar ratio n (silane coupling agent)/n (cyclosiloxane) of the cyclosiloxane to the silane coupling agent is 0.1 to 10.
7. The preparation method of claim 1, wherein the reaction temperature of the hydrolytic condensation and the prepolymerization reaction is 70-100 ℃ and the reaction time is 1-8 h.
8. The method according to claim 1, wherein the copolymerization and equilibrium ring-opening polymerization reaction is carried out at a reaction temperature of 50 to 180 ℃ and a reaction time of 0.5 to 24 hours.
9. The process according to claim 1, characterized in that the removal of water and alcohols is carried out by distillation under reduced pressure, under the following conditions: 50-180 ℃ and the vacuum degree is less than or equal to 0.09 MPa.
10. The process according to claim 9, characterized in that the removal of water and alcohols is carried out by distillation under reduced pressure, under the following conditions: 50-120 ℃ and the vacuum degree is less than or equal to 0.02 MPa.
11. The preparation method according to claim 1, characterized in that the removal of small molecular substances is carried out by distillation under reduced pressure under the following conditions: 50-180 ℃ and the vacuum degree is less than or equal to 0.09 MPa.
12. The preparation method according to claim 11, wherein the removal of the small molecular substances is carried out by distillation under reduced pressure under the following conditions: 140 ℃ and 180 ℃ and the vacuum degree is less than or equal to 0.02 MPa.
13. The method of claim 1, wherein the cyclosiloxane has the structure shown below:
wherein:
n + m is more than or equal to 3, and n and m are integers more than or equal to 0;
R1、R2、R3、R4are each R' (CH)2)xThe same or different groups represented;
x is an integer of more than or equal to 0, R' is one or a combination of more of hydrogen atom, amino group, sulfhydryl group, carboxyl group, halogen atom, phenyl group, trifluoropropyl group, epoxy group, vinyl group, piperazinyl group, N- (beta-aminoethyl) -gamma-aminopropyl group, gamma-glycidoxypropyl group or gamma-methacryloxy group.
14. The method of claim 13, wherein R is1、R2、R3、R4Respectively one or more of aminopropyl, carboxyl, mercaptopropyl, methyl, vinyl or phenyl.
15. The preparation method of claim 13, wherein the cyclosiloxane is one or a mixture of cyclotrisiloxane and cycloeicosasiloxane.
16. The preparation method according to claim 13, wherein the cyclosiloxane is a mixture of one or more cyclosiloxanes with n + m ranging from 3 to 10.
17. The method of claim 1, wherein R is5、R6Is methyl or ethyl.
18. The method of claim 1, wherein the catalyst is an organic base, an inorganic base, an organometallic base, a strong protic acid, a lewis acid, or an acidic solid.
19. The method of claim 18, wherein the catalyst is NaOH, KOH, LiOH, Me4NOH、Et4NOH、Bu4POH, sulfuric acid, sulfonic acid, perchloric acid, ferric chloride, stannic chloride, ion exchange resins, or acid clay.
20. The preparation method of claim 1, wherein the media breaking method comprises the following steps: heating to 130 deg.C or higher to decompose the temporary catalyst, filtering to remove solid catalyst or adding neutralizing agent.
21. The method of claim 20, wherein the neutralizing agent is acetic acid, sulfuric acid, phosphoric acid, hydrochloric acid, triethylamine, ethylenediamine, ammonia, sodium hydroxide, or potassium hydroxide.
22. A multifunctional alkoxy-terminated polysiloxane polymer obtained by the production method according to any one of claims 1 to 21.
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